Thermally-responsive record material

ABSTRACT

The present invention is a novel thermally-responsive record material comprising a substrate having provided thereon in substantially contiguous relationship an electron donating dye precursor, an acidic developer material, a compound of the formula  
                 
 
     wherein P is selected from  
                 
 
     wherein R 1 , R 2  and R 3  are independently selected from hydrogen, alkyl, alkoxy, aryl, aralkyl, aralkoxy, halogen, and alkoxyalkoxy;  
     wherein R 4  is independently selected from alkoxyalkyl, alkoxyalkoxy, and aralkoxyalkoxy, and a suitable binder therefor.  
     In the context of the present invention the alkyl moieties in the alkyl, aralkyl, aralkoxy, alkoxyalkyl, alkoxyalkoxy and aralkoxyalkoxy preferably are eight carbons or less, and more preferably from one through four carbons. Substituents on aryl moieties in aryl, aralkyl, aralkoxy, and aralkoxyalkoxy groups can include hydrogen, alkyl, alkoxy and halogen. The alkyl group in these substituents also is eight carbons or less, and more preferably from one through four carbons.  
     The thermally responsive record material of the invention has the unexpected and remarkable properties of enhanced image intensity or density, and/or improved thermal response.

[0001] This application under 35 USC § 111(a) claims benefit per 35 USC§ 119(e) to application Ser. No. 60/174,396 filed Jan. 5, 2000 as aprovisional application 35 USC § 111(b).

BACKGROUND OF THE INVENTION

[0002] 1. Field of the Invention

[0003] This invention relates to thermally-responsive record material.It more particularly relates to such record material in the form ofsheets or rolls coated with color-forming material comprisingchromogenic material (electron-donating dye precursor) and acidic colordeveloper material. This invention particularly concerns athermally-responsive record material (thermal record material) capableof forming a non-reversible image resistant to fade or erasure. Theinvention teaches record materials having improved thermal response,image formation, image retention and/or image density.

[0004] 2. Description of Related Art

[0005] Thermally-responsive record material systems are well known inthe art and are described in many patents, for example U.S. Pat. Nos.3,539,375; 3,674,535; 3,746,675; 4,151,748, 4,181,771; 4,246,318; and4,470,057 which are hereby incorporated by reference. In these systems,basic chromogenic material and acidic color developer material arecontained in a coating on a substrate which, when heated to a suitabletemperature, melts or softens to permit the said materials to react,thereby producing a colored mark.

[0006] Thermally-responsive record materials have characteristic thermalresponses, desirably producing a colored image upon selective thermalexposure.

[0007] In the field of thermally-responsive record material, thermalresponse is defined as the temperature at which a thermally-responsivematerial produces a colored image of sufficient intensity or density.The desired temperature of imaging varies with type of application ofthe thermally-responsive product and the equipment used in the imagingprocess. The ability to shift the temperature at which thermal image ofsufficient intensity or density is produced for any given combination ofchromogenic material and developer materials is a much sought after andvery valuable feature. For example, recent advances in high speed textor image recording demand both high speed recording devices andcorresponding thermally-responsive recording materials with sufficientthermal response that are capable of producing a high intensity or highdensity color image at low thermal energy.

[0008] Also, in the field of thermally-responsive record material, theability to increase the efficiency of the thermal image formationprocess has decided advantages. First among these is the ability toobtain the same image intensity or density with lower amount ofreactants or, alternatively, to obtain a more intense image with thesame amount of reactants.

[0009] It is an object of this invention to provide athermally-responsive material having enhanced image intensity or densityand/or improved thermal response.

DETAILED DESCRIPTION

[0010] The present invention is a novel thermally-responsive recordmaterial comprising a support having provided thereon in substantiallycontiguous relationship an electron donating dye precursor, an acidicdeveloper material, a compound of the formula

[0011] wherein P is selected from

[0012] wherein R₁, R₂ and R₃ are independently selected from hydrogen,alkyl, alkoxy, aryl, aralkyl, aralkoxy, halogen, and alkoxyalkoxygroups;

[0013] wherein R₄ is independently selected from alkoxyalkyl,alkoxyalkoxy, and aralkoxyalkoxy groups, and a suitable binder therefor;

[0014] when P is naphthalene, R₁, R₂ and R₃ in addition to theforegoing, can also include aralkoxyalkoxy groups.

[0015] In the context of the present invention the alkyl moieties in thealkyl, aralkyl, aralkoxy, alkoxyalkyl, alkoxyalkoxy and aralkoxyalkoxypreferably are each independently eight carbons or less, and morepreferably from one through four carbons. Substituents on aryl moietiesin aryl, aralkyl, aralkoxy, and aralkoxyalkoxy groups can eachindependently include hydrogen, alkyl, alkoxy and halogen. The alkylgroup in these substituents also is each independently eight carbons orless, and more preferably from one through four carbons.

[0016] More particularly, the present invention is a novelthermally-responsive record material comprising a support havingprovided thereon in substantially contiguous relationship an electrondonating dye precursor, and acidic developer material, a compound of theformula

[0017] Wherein in formulas II and III, R₁, R₂ and R₃ are independentlyselected from hydrogen, alkyl, alkoxy, aryl, aralkyl, aralkoxy, halogen,alkoxyalkoxy, and alkoxyalkoxy groups.

[0018] Wherein in formula II and III, R₄ is independently selected fromalkoxyalkyl, alkoxyalkoxy, and aralkoxyalkoxy groups, and a suitablebinder therefor.

[0019] In formula III, R₁, R₂ and R₃ can in addition to the foregoing beindependently selected from aralkoxyalkoxy groups.

[0020] In the context of the present invention the alkyl moieties in thealkyl, aralkyl, aralkoxy, alkoxyalkyl, alkoxyalkoxy and aralkoxyalkoxypreferably are each independently eight carbons or less, and morepreferably from one through four carbons. Substituents on aryl moietiesin aryl, aralkyl, aralkoxy, and aralkoxyalkoxy groups can eachindependently include hydrogen, alkyl, alkoxy and halogen. The alkylgroup in these substituents also is each independently eight carbons orless, and more preferably from one through four carbons.

[0021] The thermally responsive record material of the invention has theunexpected and remarkable properties of enhanced image intensity ordensity, and/or improved thermal response. The compounds disclosedherein as formula I, II or III desirably function as sensitizers ormodifiers facilitating reaction between the mark forming componentsyielding a more intense image at lowered temperatures or faster imaging.

[0022] In the field of thermally-responsive record material, thermalsensitivity (response) is defined as the temperature at which athermally-responsive material produces a colored image of satisfactoryintensity (density). Background is defined as the amount of colorationof a thermally-responsive record material before imaging and/or in theunimaged areas of an imaged material. The ability to maintain thethermal sensitivity of a thermally responsive material while reducingthe background coloration is a much sought after and very valuablefeature.

[0023] These and other advantages are obtained from these compounds ofthe invention.

[0024] Increases in thermally-responsive material have been achievedthrough the incorporation of a sensitizing material in the color-formingcomposition along with the chromogenic material and acidic developermaterial. Examples of sensitizing materials are as follows: fatty acidssuch as stearic acid and behenic acid, amides of fatty acids such asstearamide, metallic salts of fatty acids such as zinc stearate,aluminum stearate, calcium stearate, zinc palmitate and zinc behenate,4-benzylbiphenyl, triphenylmethane, benzyl 4-benzyloxybenzoate,2-benzyloxynaphthalene, phenyl 2-naphthoate, 1,2-diphenoxyethane,1,2-bis (3-methylphenoxy)ethane, 1,2-bis(4-methylphenoxy)ethane,4-hydroxyoctadecanilide. The compounds of the invention are a new classof sensitizers.

[0025] Compounds illustrative of the invention according to formula I,II and III include without limitation:

[0026] In general, the compounds according to formulas I, II or III canbe synthesized from a corresponding substituted or unsubstitutedbenzyloxyalkanol or alkoxyalkanol.

[0027] The alcohol is first converted to tosylate usingp-toluenesulfonyl chloride (TsCl) and aqueous sodium hydroxide inacetonitrile, keeping the temperature of the reaction mixture belowabout 55° C. by slow addition of the base. Then, the tosylate is reactedwith the corresponding phenol at 80° C. for about five hours to give thefinal product.

[0028] The times and the temperatures in this general protocol areapproximate, and the person skilled in the art can readily adjust thereaction conditions, depending on the moieties involved, to obtain thedesired product.

[0029] More specific illustrative processes for synthesis of thespecific compounds according to formulas I, II and III are set forth inmore detail in synthesis example 1.

[0030] In the heat sensitive record material according to the invention,the compound according to formulas I, II or III is preferably used in anamount corresponding to 10 to 1000 parts by weight per 100 parts of theelectron donating dye precursor though when blended with othersensitizers, the amount of the compound according to formulas I, II orIII can optionally be used in reduced amounts.

[0031] The record material includes a substrate or support materialwhich is generally in sheet form. For purposes of this invention, sheetscan be referred to as support members and are understood to also meanwebs, ribbons, tapes, belts, films, cards and the like. Sheets denotearticles having two large surface dimensions and a comparatively smallthickness dimension. The substrate or support material can be opaque,transparent or translucent and could, itself, be colored or not. Thematerial can be fibrous including, for example, paper and filamentoussynthetic materials. It can be a film including, for example, cellophaneand synthetic polymeric sheets cast, extruded, or otherwise formed. Thegist of this invention resides in the color-forming composition coatedon the substrate. The kind or type of substrate material is notcritical.

[0032] The components of the color-forming system are in substantially acontiguous relationship, substantially homogeneously distributedthroughout the coated layer or layers of material deposited on thesubstrate.

[0033] The term substantially contiguous relationship is understood tomean that the color-forming components are positioned in sufficientproximity such that upon melting, softening or subliming one or more ofthe components, a reactive color forming contact between the componentsis achieved. As is readily apparent to the person of ordinary skill inthis art, these reactive components accordingly can be in the samecoated layer or layers, or isolated or positioned in separate layers. Inother words, one component can be positioned in the first layer, andreactive or sensitizer components or the compound according to FormulasI, II or III, or an acidic developer or color former positioned in asubsequent layer or layers. The coating can optionally be applied to allof the substrate or spot printed on a certain portion. All sucharrangements are understood herein as being “substantially contiguous.”

[0034] Also, in the field of thermally-responsive record materials,there are well-known modifications in the coating structure. Forexample, a top-coating layer may be applied over a thermally-responsivelayer as a protection for the latter, or a subcoating layer may beapplied between the thermally-responsive layer and the support.Furthermore, some thermally-responsive record materials have both thetopcoat and the subcoat in their design. The topcoat and subcoat may beeither single-layered or multi-layered.

[0035] In manufacturing the record material, a coating composition isprepared which includes a fine dispersion of the components of thecolor-forming system, polymeric binder material, surface active agentsand other additives in an aqueous coating medium. The composition canadditionally contain inert pigments, such as clay, talc, aluminumhydroxide, calcined kaolin clay and calcium carbonate; syntheticpigments, such as urea-formaldehyde resin pigments; natural waxes suchas Carnuba wax; synthetic waxes; lubricants such as zinc stearate;wetting agents; defoamers, and antioxidants. Other sensitizers can alsobe included. These sensitizers for example, can includeacetoacetyl-o-toluidide, phenyl-1-hydroxy-2-naphthoate,1,2-diphenoxyethane, and p-benzylbiphenyl or any of the sensitizingmaterial listed earlier herein. Optionally, the record material can betopcoated or use subcoats such as insulating layers or hollow spheres.The color-forming system components are substantially insoluble in thedispersion vehicle (preferably water) and are ground to an individualaverage particle size of between about 1 micron to about 10 microns,preferably about 1-3 microns. The polymeric binder material issubstantially vehicle soluble although latexes are also eligible in someinstances. Preferred water soluble binders include polyvinyl alcohol,hydroxyethylcellulose, methylcellulose, methyl(hydroxypropyl) cellulose,starch, modified starches, gelatin and the like. Eligible latexmaterials include polyacrylates, styrene-butadiene-rubber latexes,polyvinylacetates, polystyrene, and the like. The polymeric binder isused to protect the coated materials from brushing and handling forcesoccasioned by storage and use of thermal sheets. Binder should bepresent in an amount to afford such protection in an amount less thanwill interfere with achieving reactive contact between color-formingreactive materials.

[0036] Coat weights can effectively be about 3 to about 9 grams persquare meter (gsm) and preferably about 5 to about 6 gsm. The practicalamount of color-forming materials is controlled by economicconsiderations, functional parameters and desired handlingcharacteristics of the coated sheets.

[0037] Electron-donating dye precursors are also known as compounds.These electron donating dye cursors or chromogens include chromogeniccompounds such as the phthalide, leucoauramine and fluoran compounds.These chromogenic materials or electron donating dye precursors are wellknown color-forming compounds for use in color-forming record systems.Examples of the compounds include Crystal Violet Lactone(3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide, (U.S. Pat. No.RE 23,024); phenyl-, indolyl, pyrrolyl, and carbazolyl-substitutedphthalides (for example, in U.S. Pat. Nos. 3,491,111; 3,491,112;3,491,116; 3,509,174); nitro-, amino-, amido-, sulfonamido-,aminobenzylidene-, halo-, anilino-substituted fluorans (for example, theU.S. Pat. Nos. 3,624,107; 3,627,78; 3,641,011; 3,642,828; 3,681,390);spirodipyrans (U.S. Pat. No. 3,971,808); and pyridine and pyrazinecompounds (for example, in U.S. Pat. Nos. 3,775,424 and 3,853,869).Other specifically eligible chromogenic compounds, not limiting theinvention in any way, are: 3-diethylamino-6-methyl-7-anilino-flouran(U.S. Pat. No. 4,510,513); 3-dibutylamino-6-methyl-7-anilino-fluoran;3-dibutylamino-7-(2-chloroanilino) fluoran;3-(N-ethyl-N-tetrahydrofurfurylamino)-6-methyl-7-3,5′6-tris(dimethylamino)spiro[9H-fluorene-9,1′(3′H)-isobenzofuran]-3′-one;7-(1-ethyl-2-methylindole-3-yl)-7-(4-diethylamino-2-ethoxyphenyl)-5,7-dihydrofuro[3,4-b]pyridin-5-one (U.S. Pat. No. 4,246,318);3-diethylamino-7-(2-chloroanilino)fluoran (U.S. Pat. No. 3,920,510);3-(N-methylcyclohexylamino)-6-methyl-7-anilinofluoran (U.S. Pat. No.3,959,571);7-(1-octyl-2-methylindole-3-yl)-7-(4-diethylamino-2-ethoxyphenyl)-5,7-dihydrofuro[3,4-b]pyridin-5-one;3-diethylamino-7,8-benzofluoran;3,3-bis(1-ethyl-2-methylindole-3-yl)phthalide;3-diethylamino-7-anilinofluoran; 3-diethylamino-7-benzylaminofluoran;3′-phenyl-7-dibenzylamino-2,2′-spirodi-[2H-1-benzopyran] and mixtures ofany of the following.

[0038] Examples of eligible acidic developer material include thecompounds listed in U.S. Pat. No. 3,539,375 as phenolic reactivematerial, particularly the monophenols and diphenols. Eligible acidicdeveloper material also includes, without being considered as limiting,the following compounds which may be used individually or in mixtures:4,4′-isopropylidinediphenol (Bisphenol A); p-hydroxybenzaldehyde;p-hydroxybenzophenone; p-hydroxypropiophenone;2,4-dihydroxybenzophenone; 1,1-bis(4-hydroxyphenyl)cyclohexane;salicylanilide; 4-hydroxy-2-methylacetophenone; 2-acetylbenzoic acid;m-hydroxyacetanilide; p-hydroxyacetanilide; 2, 4-dihydroxyacetophenone;4-hydroxy-4′-methylbenzophenone; 4,4′-dihydroxybenzophenone;2,2-bis(4-hydroxyphenyl)-4-methylpentane; benzyl(4-hydroxyphenyl)ketone;2,2-bis(4-hydroxyphenyl)-5-methylhexane; ethyl-4,4-bis(4-hydroxyphenyl)pentanoate; isopropyl-4,4-bis (4-hydroxyphenyl) pentanoate;methyl-4,4-bis (4-hydroxyphenyl) pentanoate; alkyl-4,4-bis(4-hydroxyphenyl) pentanoate; 3,3-bis (4-hydroxyphenyl) pentane; 4,4-bis(4-hydroxyphenyl) heptane; 2,2-bis(4-hydroxyphenyl)-1-phenylpropane; 2,2-bis(4-hydroxyphenyl) butane; 2,2′-methylene-bis(4-ethyl-6-tertiarybutyl phenol); 4-hydroxycoumarin;7-hydroxy-4-methylcoumarin; 2,2′-methylene-bis(4-octyl phenol);4,4′-sulfonyldiphenol; 4,4′-thiobis(6-tertiarybutyl-m-cresol);methyl-p-hydroxybenzoate; n-propyl-p-hydroxybenzoate;benzyl-p-hydroxybenzoate. Preferred among these are the phenolicdeveloper compounds. More preferred among the phenol compounds are4,4′-isopropylindinediphenol, ethyl-4,4-bis(4-hydroxyphenyl)-pentanoate,n-propyl-4,4-bis(4-hydroxyphenyl)pentanoate, isopropyl-4,4-bis(4-hydroxyphenyl) pentanoate, methyl 4,4-bis(4-hydroxyphenyl)pentanoate, 2,2-bis (4-hydroxyphenyl)-4-methylpentane,p-hydroxybenzophenone, 2,4-dihydroxybenzophenone,1,1-bis(4-hydroxyphenyl) cyclohexane, and benzyl-p-hydroxybenzoate. Acidcompounds of other kind and types are eligible.

[0039] Examples of such other compounds are zeolites, phenolic novolakresins which are the product of reaction between, for example,formaldehyde and a phenol such as an alkylphenol, e.g., p-octylphenol,or other phenols such as p-phenylphenol, and the like; and acid mineralmaterials including colloidal silica, kaolin, bentonite, attapulgite,hallosyte, and the like. Some of the polymers and minerals do not meltbut undergo color reaction on fusion of the chromogen.

[0040] The following examples are given to illustrate some of thefeatures of the present and should not be considered as limiting. Inthese examples all parts or proportions are by weight and allmeasurement are in the metric system, unless otherwise stated.

[0041] In all examples illustrated in the present invention, adispersion of a particular system component was prepared by milling thecomponent in an aqueous solution of the binder until a particle size ofbetween about 1 micron and 10 microns was achieved. The milling wasaccomplished in an attritor or other suitable milling device. Thedesired average particle size was about 1-3 microns in each dispersion.

[0042] Although some of the examples illustrate the invention using2,2-bis (4-hydroxyphenyl)-4-methylpentane as the acidic developermaterial, the invention is readily practiced using any of the eligibleacidic developer materials listed above.

[0043] The thermally-responsive sheets were made by making separatedispersions of chromogenic material, acidic material and the compound offormula 1. The dispersions were mixed in the desired ratios and appliedto a support with a wire wound rod and dried. Other materials such asfillers, antioxidants, lubricants and waxes can be added if desired. Thesheets may be calendered to improve smoothness.

[0044] The thermal images are measured using a McBeth RD-922densitometer. The densitometer is calibrated such that 0.08 indicatespure white and 1.79 a fully saturated black image.

[0045] Dispersions can be prepared in a quickie mill, attritor and smallmedia mill. Optionally, but preferably dispersants can be added such asNopco NDW at about 0.1 parts. This material is a sulfonated castor oilproduced by Nopco Chemical Company. Surfynol 104 which is a di-tertiaryacetylene glycol surface active agent produced by Air Products andChemicals, Inc. could also be included, for example at about 0.4 parts.Additionally, water-soluble polymers other than polyvinyl alcohol (PVA)may be used to prepare the dispersions.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0046] In the following example, a general procedure is described forpreparing compounds according to the invention. The examples are notintended to be exhaustive and the moieties, as previously defined, areall eligible for use in any combination in preparing the compounds.Unless otherwise noted, all measurements, percentages and parts are byweight.

SYNTHESIS EXAMPLE 1 Preparation of2-(Benzyloxy)ethyl-[4-(benzyloxy)phenyl]ether (Compound A)

[0047] 2-(Benzyloxy)ethanol (61.0 g, 0.4 mole, and p-toluenesulfonylchloride (80.0 g, 0.4 mole) were added with stirring to acetonitrile (20ml) in a liter, four-necked, round-bottom flask, equipped with amechanical stirrer, reflux condenser, thermometer and a dropping funnel.Aqueous sodium hydroxide (40.0 g, 1.0 mole/80 ml of water) was addedslowly from the dropping funnel while the temperature of the reactionmixture was kept below 55° C. After the addition was complete, thereaction mixture was stirred for one hour as it cooled to roomtemperature. Then, 4-(benzyloxy)phenol (80.0g, 0.4 mole) was added andthe reaction mixture (OV-1 column, 100° C. for 2 minutes, 25° C./min to300° C.) showed that the reaction was complete.

[0048] The reaction mixture was poured into ice/water mixture andstirred. The precipitated solid was filtered and washed with cold water,dried and dissolved in toluene. The toluene solution was washed withaqueous sodium hydroxide (10%) and water; dried and concentrated. Thecrude product was dissolved in toluene solution was passed through acolumn of alumina using toluene as eluant. Fractions containing theproduct were collected, combined and concentrated. The residue wasrecrystallized from toluene/methanol. Yield: 97.2 g (73%), white solid,M.P.: 73-75° C.) Parts Components Dispersion A - Chromogenic MaterialChromogenic Material 32.0 Binder, 20% solution of Polyvinyl alcohol inwater 27.4 Defoaming and dispersing agents 0.4 Water 40.2 DispersionA1 - Chromogenic Material is ODB-23-Di(n-butylamino)-6-methyl-7-anilinofluoran Dispersion A1 - ChromogenicMaterial is ETAC 3-(N-Ethyl-N-p-tolylamino)-6-methyl-7-anilinofluoranDispersion B - Acidic Material Acidic Material 42.5 Binder, 20% solutionof Polyvinyl alcohol in water 21.2 Defoaming and dispersing agents 36.1Dispersion B1 - Acidic Material is AP-52,2-Bis(4-hydroxyphenyl)-4-methylpentane Dispersion B2 - Acidic Materialis TGSA Bis(3-allyl-4-hydroxyphenyl)sulfone Dispersion C - SensitizingMaterial Sensitizing Material 42.5 Binder, 20% solution of Polyvinylalcohol in water 21.2 Defoaming and dispersing agents 0.2 Water 36.1Dispersion C1 - Sensitizing Material is DMT Dimethyl terephthalateDispersion C2 - Sensitizing Material is pBBP p-Benzylbiphenyl DispersionC3 - Sensitizing Material is stearamide wax Dispersion C4 - SensitizingMaterial is BZLPE-3 2-(Benzyloxy)ethyl-[4-(benzyloxy)phenyl]ether(compound A) Coating Formulation 1 Dispersion A (Chromogenic) 7.6Dispersion B (Acidic) 15.0 Dispersion C (Sensitizing) 15.0 Binder, 10%solution of polyvinylalcohol in water 45.5 Filler slurry, 50% in water19.0

EXAMPLE1

[0049] Coating Formulation 1 Using

[0050] Dispersion A1 (ODB-2)

[0051] Dispersion B1 (AP-5)

[0052] Dispersion C4 (BZLPE-3)

EXAMPLE 2

[0053] Coating Formulation 1 Using

[0054] Dispersion A2 (ETAC)

[0055] Dispersion B1 (AP-5)

[0056] Dispersion C4 (BZLPE-3)

EXAMPLE 3

[0057] Coating Formulation 1 Using

[0058] Dispersion A1 (ODB-2)

[0059] Dispersion B2 (TGSA)

[0060] Dispersion C4 (BZLPE-3)

EXAMPLE 4

[0061] Coating Formulation 1 Using

[0062] Dispersion A2 (ETAC)

[0063] Dispersion B2 (TGSA)

[0064] Dispersion C4 (BZLPE-3)

COMPARATIVE EXAMPLE 1

[0065] Coating Formulation 1 Using

[0066] Dispersion A1 (ODB-2)

[0067] Dispersion B1 (AP-5)

[0068] Dispersion C1 (DMT)

COMPARATIVE EXAMPLE 2

[0069] Coating Formulation 1 Using

[0070] Dispersion A2 (ETAC)

[0071] Dispersion B1 (AP-5)

[0072] Dispersion C1 (DMT)

COMPARATIVE EXAMPLE 3

[0073] Coating Formulation 1 Using

[0074] Dispersion A1 (ODB-2)

[0075] Dispersion B1 (AP-5)

[0076] Dispersion C2 (pBBP)

COMPARATIVE EXAMPLE 4

[0077] Coating Formulation 1 Using

[0078] Dispersion A2 (ETAC)

[0079] Dispersion B1 (AP-5)

[0080] Dispersion C2 (pBBP)

COMPARATIVE EXAMPLE 5

[0081] Coating Formulation 1 Using

[0082] Dispersion A1 (ODB-2)

[0083] Dispersion B1 (AP-5)

[0084] Dispersion C3 (stearamide wax)

COMPARATIVE EXAMPLE 6

[0085] Coating Formulation 1 Using

[0086] Dispersion A2 (ETAC)

[0087] Dispersion B1 (AP-5)

[0088] Dispersion C3 (stearamide wax)

COMPARATIVE EXAMPLE 7

[0089] Coating Formulation 1 Using

[0090] Dispersion A1 (ODB-2)

[0091] Dispersion B2 (TGSA)

[0092] Dispersion C1 (DMT) Coating Formulation 2 Parts Dispersion A(Chromogenic) 7.6 Dispersion B (Acidic) 15.0 Dispersion C (Sensitizing)0.0 Binder, 10% solution of polyvinylalcohol in water 45.5 Fillerslurry, 50% in water 19.0

COMPARATIVE EXAMPLE 13

[0093] Coating Formulation 2 Using

[0094] Dispersion A1 (ODB-2)

[0095] Dispersion B1 (AP-5)

COMPARATIVE EXAMPLE 14

[0096] Coating Formulation 2 Using

[0097] Dispersion A2 (ETAC)

[0098] Dispersion B1 (AP-5)

COMPARATIVE EXAMPLE 15

[0099] Coating Formulation 2 Using

[0100] Dispersion A1 (ODB-2)

[0101] Dispersion B2 (TGSA)

COMPARATIVE EXAMPLE 16

[0102] Coating Formulation 2 Using

[0103] Dispersion A2 (ETAC)

[0104] Dispersion B2 (TGSA)

[0105] The examples were coated at 3.0 gm/m². A PVA topcoat was appliedat 3.5 gm/m2 . The examples were then printed on the ATLANTEK model 300.The optical density was measured using a McBeth II densitometer. Theresults are in the following chart. McBeth Intensity at McBeth Intensityat Example # 12.0 mj/mm² 31.8 mj/mm² 1 0.56 1.38 2 0.26 1.30 3 0.99 1.444 0.73 1.40 Comparative 1 0.23 1.40 Comparative 2 0.10 1.30 Comparative3 0.28 1.40 Comparative 4 0.11 1.01 Comparative 5 0.31 1.39 Comparative6 0.10 1.43 Comparative 7 0.44 1.43 Comparative 8 0.18 1.32 Comparative9 0.36 1.42  Comparative 10 0.27 1.33  Comparative 11 0.52 1.43 Comparative 12 0.17 1.14  Comparative 13 0.20 1.28  Comparative 14 0.110.96  Comparative 15 0.32 1.36  Comparative 16 0.11 0.83

[0106] The principles, preferred embodiments, and modes of preparationthe present invention have been described in the foregoingspecification. The invention which is intended to be protected herein,however, it is not to be construed as limited to the particular formsdisclosed, since these are to be regarded as illustrative rather thanrestrictive. Variations and changes can be made by those skilled in theart without departing from the spirit and scope of the invention.

We claim:
 1. A thermally-responsive record material comprising a substrate having provided thereon in substantially contiguous relationship an electron donating dye precursor, an acidic developer material, a compound of the formula:

wherein P is selected from

wherein R₁, R₂, and R₃ are each independently selected from hydrogen, alkyl, alkoxy, aryl, aralkyl, aralkoxy, halogen, and alkoxyalkoxy, wherein R₄ is independently selected from alkoxyalkyl, alkoxyalkoxy and aralkoxyalkoxy, said alkyl moieties each independently being from one to eight carbons, said aryl moieties each independently being unsubstituted or substituted by alkyl (C₁-C₈), alkoxy (C₁-C₈) or halogen, and a suitable binder therefor.
 2. A thermally-responsive record material comprising a substrate having provided thereon in substantially contiguous relationship an electron donating dye precursor, an acidic developer material, a compound of the formula:

wherein R₁, R₂, and R₃ are each independently selected from hydrogen, alkyl, alkoxy, aryl, aralkyl, aralkoxy, halogen, and alkoxyalkoxy, wherein R₄ is independently selected from alkoxyalkyl, alkoxyalkoxy and aralkoxyalkoxy, said alkyl moieties each independently being from one to eight carbons, said aryl moieties each independently being unsubstituted or substituted by alkyl ((C₁-C₈)), alkoxy (C₁-C8) or halogen, and a suitable binder therefor.
 3. The thermally-responsive record material according to claim 2 wherein the compound according to formula II is


4. The thermally-responsive record material according to claim 2 wherein the compound according to formula II is


5. The thermally-responsive record material according to claim 2 wherein the compound according to formula II is


6. A thermally-responsive record material comprising a substrate having provided thereon in substantially contiguous relationship an electron donating dye precursor, an acidic developer material, a compound of the formula:

wherein R₁ and R₂ and R₃ are each independently selected from hydrogen, alkyl, alkoxy, aryl, aralkyl, aralkoxy, halogen, alkoxyalkoxy and aralkoxyalkoxy, wherein R₄ is independently selected from alkoxyalkyl, alkoxyalkoxy and aralkoxyalkoxy, said alkyl moieties each independently being from one to eight carbons, said aryl moieties each independently being unsubstituted or substituted by alkyl (C₁-C₈), alkoxy (C₁-C₈) or halogen, and a suitable binder therefor.
 7. The thermally-responsive record material according to claim 6, wherein the compound according to formula III is


8. The thermally-responsive record material according to claim 6, wherein the compound according to formula III is


9. The thermally-responsive record material according to claim 6, wherein the compound according to formula III is


10. The thermally-responsive record material according to claim 6, wherein the compound according to formula III is


11. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is


12. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is


13. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is


14. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is


15. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is


16. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is


17. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is


18. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is


19. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is


20. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is


21. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is


22. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is


23. The thermally-responsive record material according to claim 3 wherein the compound according to formula III is


24. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is


25. The thermally-responsive record material according to claim 6 wherein the compound according to formula III is 